Waterproofing agents for textile finishing

ABSTRACT

An aqueous emulsion containing a hydrophobicizing composition, the composition containing: (a) a zirconium salt; and (b) a fatty compound selected from the group consisting of (i) branched or unbranched, symmetrical or nonsymmetrical dialkyl ethers having from about 8 to 44 carbon atoms, (ii) ester of branched or unbranched fatty acids having from about 12 to 22 carbon atoms with branched or unbranched fatty alcohols having from about 8 to 22 carbon atoms, (iii) branched or unbranched, symmetrical or nonsymmetrical dialkyl ketones having from about 8 to 44 carbon atoms, and mixtures thereof, and wherein the aqueous emulsion has an average particle size of from about 100 to 200 nm.

BACKGROUND OF THE INVENTION

This invention relates to hydrophobicizing compositions for finishingtextiles, to a process for hydrophobicizing textiles and to the use ofcertain fatty compounds as hydrophobicizing compositions.

Textiles are generally hydrophobicized with hydrophobicizingcompositions based on polysiloxanes, fluorocarbons or mixtures ofaluminium or zirconium salts with paraffins (cf. “Handbuch derTextilhilfsmittel”, A. Chwala, V. Anger, Verlag Chemie, New York 1977,Chapter 3.24 “Phobiermittel”, pages 735 et seq). The object ofhydrophobicizing textiles, particularly weatherproof clothing, is tomake them either water-repellent or impermeable to water. Thehydrophobicizing composition is applied to the fibers of the textilesand arranges itself thereon in such a way that the hydrophobic parts ofthe molecule are perpendicular to the fiber surface. In this way, thetendency of the water to spread over the entire surface is greatlyreduced. Under the effect of the cohesion forces, the water assumes theform of spheres and runs off the textile surface in beads.

Although the hydrophobicizing compositions described in the prior art,particularly the paraffin emulsions containing zirconium salts, enabletextiles to be adequately hydrophobicized, they are attended by theproblem that they are not biodegradable or not sufficientlybiodegradable. In addition, where corresponding paraffin emulsions areapplied by padding, paraffin deposits are observed on the paddingrollers after prolonged operating times so that the rollers have to becleaned which means an expensive interruption of the production process.Accordingly, there was a need to provide hydrophobicizing compositionswhich would satisfy all the performance requirements of the textileindustry and, in particular, would produce few, if any, deposits onmachine parts and at the same time would be biodegradable.

DETAILED DESCRIPTION OF THE INVENTION

It has now been found that a combination of zirconium salts with certainfatty compounds leads to hydrophobicizing compositions which are aseffective in terms of finishing as the paraffin emulsions known per se,but which at the same time also satisfy biodegradability requirements.

In a first embodiment, the present invention relates to ahydrophobicizing composition for finishing textiles which contains azirconium salt in combination with a fatty compound selected from thegroup of

a) branched or unbranched, symmetrical or nonsymmetrical dialkyl etherscontaining a total of 8 to 44 carbon atoms and/or

b) esters of branched or unbranched C₁₂₋₂₂ fatty acids with branched orunbranched C₈₋₂₂ fatty alcohols and/or

c) branched or unbranched, symmetrical or nonsymmetrical dialkyl ketonescontaining a total of 8 to 44 carbon atoms.

Suitable zirconium salts are any of the compounds known in the prior artamong which zirconium acetate is particularly preferred.

The fatty compounds are alkyl ethers known per se with the generalformula R¹—O—R² where R¹ and R² are each alkyl groups containing 1 to 22carbon atoms. The total number of carbon atoms in the molecule is 8 to44. Both symmetrical ethers, i.e. R¹ and R² are identical, andnonsymmetrical ethers (R¹≠R²) may be used. The alkyl groups R¹ and R²may be saturated, unsaturated, branched or unbranched. Ethers where R¹and R² have a carbon chain length of 10 to 22 are particularlypreferred. The total number of carbon atoms in the ethers is preferably0 to 44. Preferred ethers are, for example, dibehenyl ether, distearylether, dipalmityl ether and dimyristyl ether. Ethyl hexyl eicosyl etheris mentioned as an example of a nonsymmetrical ether. The ethers may beproduced by any known industrial processes. A second group of suitablefatty compounds are esters of branched or unbranched C₁₂₋₂₂ fatty acidswith branched or unbranched C₈₋₂₂ fatty alcohols. Suitable fatty acidsare, for example, caprylic, pelargonic, capric, undecanoic, tridecanoic,myristic, pentadecanoic, palmitic, heptadecanoic, octadecanoic,nonanoic, arachic or behenic acid. Suitable fatty alcohols are, forexample, caprylic, capric, lauryl, myristyl, palmityl, stearyl,arachidyl or behenyl alcohol. As a third group of suitable fattycompounds, the hydrophobicizing compositions may contain dialkyl ketonescontaining a total of 8 to 44 carbon atoms with the formula R³—CO—R⁴where R³ and R⁴ each represent an alkyl group. Both symmetrical ketones(R³=R⁴) and nonsymmetrical ketones (R³≠R⁴) may be used. Suitable ketonesare, for example, alkyl methyl ketones, such as octanonan-2-one,nonan-2-one, undecan-2-one, dodecan-2-one, tridecan-2-one,tetradecan-2-one, pentadecan-2-one, heptadecan-2-one, octadecan-2-one,nonadecan-2-one, pentadecan-2-one, heptadecan-2-one, octadecan-2-one,nonadecane-2-one, eicosan-2-one or dodecasan-2-one. Symmetrical ketones,such as undecan-6-one, tridecan-7-one, pentadecan-8-one,heptadecan-9-one, nonadecan-10-one, tricosan-12-one,hentriacontan-16-one, pentatriacontan-18-one, nonatriacontan-20-one andtriatetracontan-22-one, are also suitable. The ketones can be producedby any methods known to the expert, for example by oxidation ordehydrogenation of secondary alcohols.

The hydrophobicizing compositions according to the invention arepreferably present in the form of an aqueous emulsion, water beingpresent in quantities of 10 to 90% by weight. The compositionspreferably contain 30 to 80% by weight and more particularly 40 to 60%by weight of water. The zirconium salts are generally present inquantities of 1 to 20% by weight, preferably in quantities of 5 to 15%by weight and more particularly in quantities of 5 to 10% by weight. Thefatty compounds a) to c) are preferably present in the compositions inquantities of 10 to 95% by weight, more preferably in quantities of 15to 60% by weight and most particularly in quantities of 10 to 30% byweight.

If necessary, the compositions may contain other suitable ingredientsbesides the salts and fatty compounds, more particularly emulsifiers butalso nonslip agents, wet strength improvers, feel additives, softeners,solvents, for example ethanol, n-propanol or i-propanol, and pHadjusters, such as organic acids or bases. The pH value of the aqueousemulsions is in the acidic range, preferably below 4.5 and moreparticularly in the range from 2.0 to 3.5. The auxiliaries are presentin small quantities of 0.5 to 5% by weight. In general, the compositionsaccording to the invention contain such auxiliaries in a total quantityof at most 10% by weight.

The compositions according to the invention are produced in known mannerby mixing the starting materials with water, heating the resultingmixture to temperatures of 40 to 90° C. and then homogenizing themixture. Average particle sizes of less than 250 nm should be reached.The average particle sizes are in the range from 100 to 200 nm. Aftercooling, the compositions may be used without further treatment. Thecompositions are normally applied to the textiles in the form an aqueousemulsion by padding. The compositions according to the invention aresuitable for the hydrophobic finishing of textiles of synthetic ornatural fibers, more particularly cotton textiles.

In another embodiment, the present invention relates to a process forthe hydrophobic finishing of textiles in which compositions as describedin the foregoing are suitably applied to textiles. The invention alsorelates to the use of these compositions for the hydrophobic finishingof textiles.

EXAMPLES

In order to compare the compositions according to the invention with theprior art, the following basic formulation was prepared, paraffin beingtested as the fatty compound in comparison with the group b) fattycompounds:

Formulation Fatty compound 25% by weight Emulsifier 2.8% by weightZirconium acetate 10% by weight Acetic acid 2% by weight i-Propanol 2%by weight Water 58.2% by weight

Composition Fatty compound A Paraffin Mp.: 52-54° C. (comparison) 1Distearyl ether 2 Diisotridecyl ether 3 Ethyl hexyl eicosyl ether 4Didecyl ether 5 Stearic acid stearyl ester

The compositions were prepared as follows:

The starting materials were introduced, heated to 85° C. andhomogenized. The compositions were then cooled to 20° C.

The compositions had pH values of 2.8 to 3.0. The particle size was inthe 200-250 nm range. Hydrophobicity was determined by the Schopper Test(DIN EN 20811): test fabric 100% CO (ca. 300 g/m²) finished with 150 g/lemulsion. Liquor uptake 86%. Drying at 140° C.

Results in mm water column: Composition 1st Drop 2nd Drop 3rd Drop A 360370 380 1 330 370 385 2 230 240 250 3 250 260 275 4 260 270 275 5 300320 320

Resistance to friction was tested with an endless runner (120 g/lliquor, 5 bar pressure, speed 20 m/minute). The test was terminated whendeposits were observed on the padding roller:

Time in mins. to Composition appearance of deposits A 15 1 >20 2 >20 314 4 15 5 >20

What is claimed is:
 1. An aqueous emulsion comprising a hydrophobicizingcomposition, the composition containing: (a) a zirconium salt; and (b) afatty compound selected from the group consisting of (i) branched orunbranched, symmetrical or nonsymmetrical dialkyl ethers having fromabout 8 to 44 carbon atoms, (ii) ester of branched or unbranched fattyacids having from about 12 to 22 carbon atoms with branched orunbranched fatty alcohols having from about 8 to 22 carbon atoms, (iii)branched or unbranched, symmetrical or nonsymmetrical dialkyl ketoneshaving from about 8 to 44 carbon atoms, and mixtures thereof, andwherein the aqueous emulsion has an average particle size of from about100 to 200 nm.
 2. The emulsion of claim 1 wherein the fatty compound ispresent in the composition in an amount of from about 10 to 95% byweight, based on the weight of the composition.
 3. The emulsion of claim1 wherein the fatty compound is present in the composition in an amountof from about 15 to 60% by weight, based on the weight of thecomposition.
 4. The emulsion of claim 1 to wherein the fatty compound ispresent in the composition in an amount of from about 10 to 30% byweight, based on the weight of the composition.
 5. The emulsion of claim1 wherein the zirconium salt is present in the composition in an amountof from about 1 to 20% by weight, based on the weight of thecomposition.
 6. The emulsion of claim 1 wherein the zirconium salt ispresent in the composition in an amount of from about 5 to 15% byweight, based on the weight of the composition.
 7. The emulsion of claim1 wherein the zirconium salt is present in the composition in an amountof from about 5 to 10% by weight, based on the weight of thecomposition.
 8. The emulsion of claim 1 wherein the zirconium salt iszirconium acetate.
 9. The emulsion of claim 1 wherein water is presentin the emulsion in an amount of from about 10 to 90% by weight, based onthe weight of the emulsion.
 10. A process for hydrophobicizing textilescomprising contacting the textiles with an aqueous emulsion containing ahydrophobicizing composition, the hydrophobicizing compositioncontaining: (a) a zirconium salt; and (b) a fatty compound selected fromthe group consisting of (i) branched or unbranched, symmetrical ornonsymmetrical dialkyl ethers having from about 8 to 44 carbon atoms,(ii) ester of branched or unbranched fatty acids having from about 12 to22 carbon atoms with branched or unbranched fatty alcohols having fromabout 8 to 22 carbon atoms, (iii) branched or unbranched, symmetrical ornonsymmetrical dialkyl ketones having from about 8 to 44 carbon atoms,and mixtures thereof, and wherein the aqueous emulsion has an averageparticle size of from about 100 to 200 nm.
 11. The process of claim 10wherein the fatty compound is present in the composition in an amount offrom about 10 to 95% by weight, based on the weight of the composition.12. The process of claim 10 wherein the fatty compound is present in thecomposition in an amount of from about 15 to 60% by weight, based on theweight of the composition.
 13. The process of claim 10 wherein the fattycompound is present in the composition in an amount of from about 10 to30% by weight, based on the weight of the composition.
 14. The processof claim 10 wherein the zirconium salt is present in the composition inan amount of from about 1 to 20% by weight, based on the weight of thecomposition.
 15. The process of claim 10 wherein the zirconium salt ispresent in the composition in an amount of from about 5 to 15% byweight, based on the weight of the composition.
 16. The process of claim10 wherein the zirconium salt is present in the composition in an amountof from about 5 to 10% by weight, based on the weight of thecomposition.
 17. The process of claim 10 wherein the zirconium salt iszirconium acetate.
 18. The process of claim 10 wherein water is presentin the emulsion in an amount of from about 10 to 90% by weight, based onthe weight of the emulsion.